Uniformly dyed water-swellable cellulosic fibers

ABSTRACT

Uniformly dyed water-swellable cellulosic fibers obtained by dyeing cellulosic fibers in the swollen state with a dye of the formula &lt;IMAGE&gt;   in which one R is R1, OR1, SR1 or   &lt;IMAGE&gt;  the other R is &lt;IMAGE&gt;  R1 and R2 independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical,   &lt;IMAGE&gt; may also be a saturated heterocyclic radical, and D is the radical of a diazo component. The dyed fibers exhibit very good fastness properties.

The invention relates to uniformly dyed water-swellable cellulosicfibers which are fast to washing, dry-cleaning, sublimation and lightand have been produced by contacting water-swellable cellulose fiberssequentially or concomitantly with water, ethylene glycol or aderivative thereof and, while the fibers are still swollen, anessentially water-insoluble dye of the formula I ##STR5## where one R isR¹, OR¹, SR¹ or ##STR6## the other R is ##STR7## R¹ and R² independentlyof one another are hydrogen or an aliphatic, cycloaliphatic, araliphaticor aromatic radical, ##STR8## may also be a saturated heterocyclicradical, and D is the radical of a diazo component.

The radicals D are in particular derived from amines of the benzene,naphthalene, benzthiazole, benzisothiazole, thiazole, thiadiazole,indazole, pyrazole, thiophene, azobenzene, phthalimide, naphthalimide oranthraquinone series.

Examples of substituents of the radicals D of the diazo component are:

In the benzene series: fluorine, chlorine, bromine, nitro, cyano,trifluoromethyl, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, acarboxylic acid ester group, eg. alkoxycarbonyl (where alkoxy is of 1 to8 carbon atoms), phenoxy carbonyl, phenoxyethoxycarbonyl orβ-alkoxyethoxycarbonyl (where alkoxy is of 1 to 4 carbon atoms),unsubstituted, N-monosubstituted or N,N-disubstituted carboxamide orsulfonamide, methyl, ethyl, butyl, octyl, hexyl, methoxy or ethoxy,carboxyl, 3-alkyl-1,2,4-oxdiazolyl (where alkyl is of 1 to 4 carbonatoms) and 3-phenyl-1,2,4-oxdiazolyl; examples of the N-substituents ofcarboxamide or sulfonamide are methyl, ethyl, phenyl, benzyl,phenylethyl, cyclohexyl, norbornyl, propyl, butyl, β-hydroxyethyl,γ-hydroxypropyl, β-methoxyethyl, γ-methoxypropyl and γ-ethoxypropyl, orthe amide group in question may be the pyrrolidide, piperidide ormorpholide.

In the azobenzene series: fluorine, chlorine, bromine, nitro, cyano,trifluoromethyl, methyl, ethyl, carboxyl, methoxy and ethoxy, as well asthe carboxylic acid ester, optionally substituted carbamoyl andsulfamoyl radicals mentioned in connection with the benzene series, andhydroxyl.

In any of the heterocyclic series: chlorine, bromine, nitro, cyano,methyl, ethyl, phenyl, methoxy, ethoxy, methylmercapto,β-carbomethoxyethylmercapto, β-carboethoxyethylmercapto, carbomethoxy,carboethoxy, acetyl, methylsulfonyl and ethylsulfonyl.

In the anthraquinone series: chlorine, bromine, amino, acetyl, methyl,ethyl, phenylamino, tolylamino, hydroxyl, methoxy, ethoxy, cyano andcarboxyl.

In the benzene and naphthalene series, preferred diazo components haveat least one substituent which reduces the basicity, eg. methylsulfonyl,phenylsulfonyl, ethylsulfonyl, a carboxylic acid ester group,unsubstituted or N-substituted carbamoyl, chlorine, bromine,trifluoromethyl and especially cyano.

R¹ and R² may be hydrogen or, for example, one of the followingsubstituents: alkyl of 1 to 8 carbon atoms, alkyl of 2 to 8 carbon atomssubstituted by hydroxyl, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy,tolyloxy, cyclohexoxy, β-phenylethoxy, phenoxyethoxy or benzyloxy,cyclohexyl, norbornyl, benzyl, phenylethyl, phenylhydroxyethyl,phenylpropyl, phenylbutyl, phenyl which is unsubstituted or substitutedby chlorine, methyl, trifluoromethyl, pyrrolidonyl, methoxy or ethoxy,polyalkoxyalkyl of 5 to 12 carbon atoms, hydroxypolyalkoxyalkyl of 4 to9 carbon atoms, alkanoyloxyalkyl, where alkanoyloxy is of 1 to 8 carbonatoms and alkyl is of 2 to 6 carbon atoms, aroyloxyalkyl, where aroyloxyis of 7 to 11 carbon atoms and alkyl is of 2 to 6 carbon atoms,alkylaminocarbonyloxyalkyl, where alkylamino is of 1 to 8 carbon atomsand alkyl is of 2 to 6 carbon atoms, arylaminocarbonyloxyalkyl, wherearylamino is of 6 to 10 carbon atoms and alkyl is of 2 to 6 carbonatoms, alkoxycarbonylalkyl, where alkoxy is of 1 to 8 carbon atoms andalkyl is of 2 to 7 carbon atoms, alkanoyl of 1 to 18 carbon atoms,aralkanoyl of 8 to 10 carbon atoms, aroyl of 7 to 11 carbon atoms,alkylsulfonyl of 1 to 4 carbon atoms or arylsulfonyl of 6 to 10 carbonatoms.

Specific examples of radicals R¹, in addition to those alreadymentioned, are:

1. Substituted and unsubstituted alkyl:

CH₃, C₂ H₅, n- and i-C₃ H₇, n- and i-C₄ H₉, C₆ H₁₃, ##STR9## CH₂ CH₂ OH,(CH₂)₃ OH, ##STR10## (CH₂)₄ OH, (CH₂)₆ OH, ##STR11## (CH₂)₂ O(CH₂)₂ OH,(CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₂ OH, (CH₂)₂ CN, (CH₂)₅ CN, (CH₂)₆ CN,(CH₂)₇ CN, (CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ O(CH₂)₂ CN, (CH₂)₂ O(CH₂)₂ O(CH₂)₂CN, (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅, (CH₂)₃ O(CH₂)₆ OH, (CH₂)₃OC₂ H₄ OCH(CH₃)₂, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OCH₂ C₆ H₅, (CH₂)₃OC₂ H₄ OC₂ H₄ C₆ H₅, ##STR12## CH₂ CH₂ COOH, (CH₂)₅ COOH, (CH₂)₆ COOH,the corresponding radicals in which the groups --O(CH₂)₂ --, ##STR13##occur two or three times, CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₃ H₇,CH₂ CH₂ OC₄ H₉, CH₂ CH₂ OC₆ H₅, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃H₇, (CH₂)₃ OC₄ H₉, ##STR14##

2. Substituted and unsubstituted cycloalkyl and polycycloalkyl:##STR15##

3. Aralkyl:

CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR16## and the corresponding radicals with C₆H₄ CH₃ instead of C₆ H₅.

4. Unsubstituted and substituted phenyl:

C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, C₆ H₄ OCH₂ CH₂OH and C₆ H₄ Cl.

5. The radicals:

CH₂ CH═CH₂, CH₂ COOCH₃, (CH₂)₅ COOCH₃, (CH₂)₅ COOC₂ H₅, (CH₂)₅ COOC₄ H₉,##STR17## where n is 2, 3, 4 or 6.

6. Acyloxy: (CH₂)₂ OCHO, (CH₂)₂ OCOCH₃, (C₂ H₄ O)₂ CHO, (C₂ H₄ O)₂COCH₃, (CH₂)₂ OCOC₃ H₇, ##STR18## (CH₂)₂ OCOC₆ H₅, (CH₂)₂ OCOC₆ H₄ CH₃,(CH₂)₂ OCOC₆ H₄ Cl, (CH₂)₂ OCOC₁₀ H₇, (CH₂)₂ OCONHCH₃, (CH₂)₂ OCONHC₄H₉, ##STR19## (CH₂)₂ OCONHC₆ H₅, (CH₂)₂ OCONHC₆ H₄ Cl, (CH₂)₂ OCONHC₆ H₃Cl₂, and the corresponding radicals with (CH₂)₃, (CH₂)₄ or (CH₂)₆.

Examples of preferred substituents R¹ are hydrogen, CH₃, C₂ H₅, n- andi-C₃ H₇, n- and i-C₄ H₉, C₆ H₁₃, CH₂ CH₂ OH, (CH₂)₃ OH, ##STR20## (CH₂)₄OH, (CH₂)₆ OH ##STR21## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₂ OH, (CH₂)₃O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₆ OH, ##STR22## (n=2, 3, 6), CH₂ CH₂ OCH₃, CH₂CH₂ OC₂ H₅, CH₂ CH₂ OC₄ H₉, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇,(CH₂)₃ OC₄ H₉, ##STR23## (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₄ H₉,(CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR24## CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR25## C₆ H₅,C₆ H₄ CH₃, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₄ OH and (CH₂)₅ COOH.

Examples of ##STR26## are pyrrolidino, piperidino, morpholino,piperazino and hexamethyleneimino.

The dyes of the formula I can be prepared by reacting a diazo compoundof an amine of the formula II

    d--nh.sub.2                                                ii

with a coupling component of the formula III ##STR27## where D, R, R¹and R² have the stated meaning.

The diazotization of the amines may be carried out in the conventionalmanner. The coupling may also be carried out in the conventional manner,in an aqueous, slightly to strongly acid medium, with or withoutaddition of a solvent.

In particular, the invention relates to fibers which have been dyed witha dye of the formula I, where D is phenyl which is substituted by cyano,nitro, trifluoromethyl, methyl, fluorine, chlorine, bromine,alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, oxdiazolyl,##STR28## or is anthraquinonyl which is unsubstituted or substituted bymethyl, chlorine, bromine or carboxyl, or is benzisothiazolylsubstituted by nitro, chlorine or bromine,

R¹ is hydrogen, alkyl of 1 to 8 carbon atoms, alkyl of 2 to 8 carbonatoms which is substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms,phenoxy, tolyloxy, cyclohexoxy, benzyloxy, β-phenylethoxy, carboxyl, acarboxylic acid ester group of a total of 2 to 9 carbon atoms, C-acyloxyof a total of 1 to 11 carbon atoms, alkylaminocarbonyloxy (where alkylis of 1 to 8 carbon atoms), phenylaminocarbonyloxy,tolylaminocarbonyloxy, chlorophenylaminocarbonyloxy,dichlorophenylaminocarbonyloxy or pyrrolidonyl, cyclohexyl, norbornyl,phenylalkyl (where alkyl is of 1 to 4 carbon atoms), tolylalkyl (wherealkyl is of 1 to 4 carbon atoms), β-phenyl-β-hydroxyethyl, phenyl, whichis unsubstituted or substituted by fluorine, chlorine, bromine, methyl,trifluoromethyl, ethyl, methoxy, ethoxy or pyrrolidonyl, CH₂ CH₂ OCH₂CH₂ OH or (CH₂)₃ (OC₂ H₄)_(n) OB,

n is 0, 1 or 2,

B is hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, benzyl,phenylethyl, phenyl or tolyl,

R² is hydrogen, alkyl of 1 to 8 carbon atoms, or alkyl of 2 to 9 carbonatoms substituted by hydroxyl or alkoxy of 1 to 8 carbon atoms, or

R¹ and R² together with the nitrogen are pyrrolidino, piperidino,morpholino or hexamethyleneimino,

T¹ is hydrogen, chlorine, bromine, methyl, methoxy or ethoxy,

T² is hydrogen, methyl, methoxy or ethoxy,

T³ is hydrogen, methyl, chlorine, bromine, cyano, nitro, methylsulfonyl,##STR29## or COOB¹,

B¹ is hydrogen, alkyl of 1 to 8 carbon atoms, phenylalkyl (where alkylis of 1 to 4 carbon atoms) or (OC₂ H₄)_(n) OB,

Y is --SO₂ -- or --CO--,

T⁴ is hydrogen, cyano, chlorine or bromine and

T⁵ is hydrogen, methyl or ethyl. Dyes of particular industrial value forthe dyeing of the fiber are those which contain a dye or a mixture ofdyes of the formula I a ##STR30## where D¹ is a diazo component of thebenzene, phthalimide, naphthalimide, anthraquinone or azobenzene seriesor a nitrobenzisothiazolyl radical and R and R¹ have the statedmeanings.

The substituents are advantageously chosen so that the molecule containsat least one aryl radical, preferably phenyl, either in the diazocomponent or in the coupling component.

Preferred dyes are those where at least one of the radicals R¹ containsan oxygen-containing amine radical, preferably a radical of one of theamines methoxyethylamine, methoxypropylamine, phenoxyethoxypropylamine,phenoxyethoxyethoxypropylamine, benzyloxypropylamine,phenylethoxypropylamine, butoxyethoxypropylamine, benzoyloxyethylamine,benzoyloxypropylamine, benzoyloxyethoxyethylamine, H₂ N(CH₂)₃ O(CH₂)₄OCOC₆ H₅, H₂ N(CH)₂ OCONHC₆ H₅, H₂ N(CH₂)₃ OCONHC₆ H₅ or H₂N(CH₂)OCONHC₆ H₄ Cl, and dyes where one R¹ is derived from anoxygen-containing amine and the other R¹ is phenylamino or amino.

Specific examples of amines from which the radical D¹ may be derived areo-, m- and p-cyanoaniline, 2,4-dicyanoaniline, 2,4,6-tribromoaniline,2-trifluoromethylaniline, 2,4-dichloroaniline,2-cyano-4,6-dibromoaniline, 2,4-dicyano-6-bromoaniline,4-cyano-2-chloroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene,2-chloro-5-aminobenzonitrile, 2-amino-5-chloro-benzonitrile,1-aminobenzene-4-methylsulfone,1-amino-2,6-dibromobenzene-4-methylsulfone,1-amino-2-chloro-4-methylsulfone,1-amino-2,6-dichlorobenzene-4-methylsulfone, propyl3,5-dichloroanthranilate, β-methoxyethyl 3,5-dibromoanthranilate,4-aminoacetophenone, 4- and 2-aminobenzophenone, anthranilate,4-aminoacetophenone, 4- and 2-aminobenzophenone, 2- and4-aminodiphenylsulfone, 3- and 4-aminophthalic acid β-hydroxyethylimide,phenylimide and p-tolylimide, 3-amino-6-chlorophthalimide and itsN-substitution products, 3-amino-4-cyano-5-methyl- and-ethyl-phthalimide and their N-substitution products,1-amino-2-chloroanthraquinone, 1-amino-2-bromoanthraquinone,1-amino-2,4-dibromoanthraquinone,1-amino-2-acetyl-4-chloroanthraquinone,1-amino-anthraquinone-6-carboxylic acid,1-amino-anthraquinone-6-carboxylic acid ethyl ester,1-amino-4-methoxy-anthraquinone, 1-amino-4-hydroxyanthraquinone,1-amino-2-chloro-4-p-toluidino-anthraquinone,2-amino-1-chloro-anthraquinone, 2-amino-3-chloroanthraquinone,2-amino-3-bromoanthraquinone, 2-amino-1,3-dibromoanthraquinone,2-amino-1-cyano-3-bromoanthraquinone, 1-, 6- and 7-aminobenzanthrone, 1-and 2-amino-anthraquinone, 1-amino-4-chloroanthraquinone,2,4-dicyano-3,5-dimethylaniline, 4-aminonaphthalic acid imide,methylimide, n-butylimide, 2-hydroxyethylimide, 3'-methoxypropylimideand phenylimide, 5-nitro-3-amino-2,1-benzisothiazole and5-nitro-7-bromo-3-amino-2,1-benzisothiazole.

Examples of suitable diazo components of the aminoazobenzene series are:4-aminoazobenzene, 3-chloro-4-aminoazobenzene,3-bromo-4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene,3',2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene,2-methyl-5-methoxy-4-aminoazobenzene,2-methyl-4',5-dimethoxy-4-aminoazobenzene,4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene,4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene,4'-chloro-2,5-dimethoxy-4-aminoazobenzene,4'-chloro-2,5-dimethyl-4-aminobenzene,4'-methoxy-2,5-dimethyl-4-aminoazobenzene,3,5-dibromo-4-aminoazobenzene, 2,3'-dichloro-4-aminoazobenzene,3-methoxy-4-aminoazobenzene, 2',3-dimethyl-5-bromo-4-aminoazobenzene,4'-amino-2',5'-dimethylazobenzene-4-sulfonamide and-3-sulfonamide, andthe aminoazobenzenes of the formula ##STR31## where T¹ is hydrogen,chlorine, bromine, methoxy or methyl, T² is hydrogen, methoxy or methylT³ is nitro or ##STR32## or COOB¹, T⁴ is hydrogen, chlorine, bromine orcyano, Y is --CO-- or --SO₂ --, B¹ is an alcohol radical and R¹ and R²have the stated meaning.

From the point of view of their structure, the dyes of the formula I maybe described as disperse dyes, which as a rule cannot be applied to, forexample, cotton. However, U.S. Pat. No. 3,706,525 describes a processwhich permits printing such dyes on cellulose and cellulose-containingtextile material. The disclosures in the said patent with regard toprocess conditions also apply in principle to the dyes of formula I. Inaddition, German Patent Applications P 25 24 243.7 and P 25 28 743.8disclose further processes by means of which the dyes of formula I canbe applied. Amongst these, printing processes are preferred. The abovepatent and patent applications are incorporated herein by reference.

The dyes of formula I are advantageously applied in the form of dyeformulations, whereby dyeings and prints with excellent fastnessproperties are obtained, amongst which the wetfastness and in some casesalso the lightfastness should be singled out. In the case of prints, forexample, washing does not result in staining of any white ground whichmay be present.

The dye formulations contain the dyes of the formula I together withdispersants, water-retaining agents and water, with or without othercomponents conventionally used in dye formulations, eg. disinfectants oranti-foam agents.

Suitable dispersants are cationic compounds and, preferably, non-ionicand, in particular, anionic compounds, ie. the dispersantsconventionally used for disperse dyes.

Specific examples are ligninsulfonates, sulfomethylation products ofphenol, condensation products of phenolsulfonic acids, phenol,formaldehyde and urea, condensation products of β-sulfonaphthalene andformaldehyde, and polyadducts of propylene oxide and ethylene oxide withethylene glycol, propylene glycol or ethylenediamine.

Water-retaining agents are, in particular, glycols and glycol ethers,eg. ethylene glycol, propylene glycol, diethylene glycol and ethyleneglycol monomethyl ether.

In the Examples which follow, parts and percentages are by weight,unless stated otherwise.

EXAMPLE 1

A cotton fabric is printed by rotary screen printing with an ink whichcomprises 10 parts of the dye of the formula ##STR33## 100 parts of apolyethylene oxide of molecular weight 300 and 790 parts of a 3%strength alginate thickener, and the print is dried at 100° C. The printis then treated for 1 minute with hot air at 200° C., rinsed cold,soaped at the boil, again rinsed cold and dried. A lightfast andwashfast yellow print on a white ground is obtained.

EXAMPLE 2

A polyester/cotton union fabric (weight ratio 67:35 (sic)) is printedwith a paste which comprises 20 parts of the dye of the formula##STR34## 120 parts of the reaction product of a polyethylene oxide ofmolecular weight 300 with boric acid in the molar ratio of 3:1 and 860parts of a 10% strength alginate thickener. The print is dried at 105°C. and treated for 6 minutes with live steam at 180° C. It is thenrinsed with cold water, soaped at 80° C., rinsed cold and dried.

A lightfast and washfast red print on a white ground is obtained.

EXAMPLE 3

A cotton fabric is roller-printed with a print paste which comprises 15parts of the dye of the formula ##STR35## 110 parts of a polyethyleneoxide of molecular weight 350, 30 parts of oleic acid diethanolamide and845 parts of a 10% strength alginate thickener. The print is dried at100° C. and then fixed by treatment with hot air at 195° C. for 1minute. It is finished as described in Example 1 and a fast goldenyellow print on a white ground is obtained.

EXAMPLE 4

A polyester/cotton union fabric (weight ratio 67:33) is printed, on ascreen printing machine, with an ink which comprises 30 parts of the dyeof the formula ##STR36## 100 parts of the reaction product of apolyethylene oxide of molecular weight 300 with boric acid in the molarratio of 3:1, 30 parts of oleic acid diethanolamide and 840 parts of a3% strength alginate thickener, and the print is dried at 110° C. It isthen treated for 5 minutes with live steam at 185° C. and is finished asdescribed in Example 2.

A fast yellowish red print on a white ground is obtained.

EXAMPLE 5

A cotton fabric is padded with a solution which contains 20 parts of thedye of the formula ##STR37## 300 parts of a 3% strength alginatethickener, 550 parts of water and 130 parts of a polyethylene oxide ofmolecular weight 300. The wet pick-up of the fabric is set at 80%. Thefabric is dried at 100° C. To fix the dye, it is treated for 5 minuteswith live steam at 190° C. The fabric is then rinsed cold and washed at90° C. in a bath which contains 3 parts of a condensation product of along-chain alcohol with ethylene oxide per 997 parts of water.

A yellow dying is obtained.

Instead of a cotton fabric, a polyester/cotton union fabric (weightratio 67:33) can be padded with the above solution. A yellow dyeing inwhich both types of fiber have the same hue is obtained. Fixing with hotair for 2 minutes at 195° C. may be substituted for the live steamtreatment.

EXAMPLE 6

A cotton fabric is padded with a solution of 150 parts of polyethyleneoxide in 850 parts of water to give a wet pickup of 80%, and the paddedfabric is dried at 100° C. This pretreated fabric is printed by rotaryscreen printing with an ink which comprises 30 parts of the dye of theformula ##STR38## and 970 parts of a 10% strength alginate thickener.The print is dried at 105° C., treated with live steam at 185° C. for 7minutes and then finished by rinsing and soaping as described in Example1.

A fast red print on a white ground is obtained.

The dyes mentioned in the Examples below can be converted to acommercial dye formulation as follows: 30 parts of the dye (which may bein the form of a concentrated solution in dimethylformamide orpolyethylene glycols), 6 parts of a dispersant, 10 parts of awater-retaining agent, 1 part of a disinfectant and about 53 parts ofwater are milled in a stirred ball mill until the particle size is about0.5 μm. This gives a dye dispersion which is stable on storage.

EXAMPLE 7

20 parts of 4-aminoazobenzene are stirred thoroughly with 120 parts ofwater and 2 parts of oxyethylated sperm oil alcohol and the suspensionis diluted with 30 parts by volume of concentrated hydrochloric acid andstirred for a further 30 minutes. It is then brought to 800 parts byvolume with water and 34 parts by volume of a 23% strength aqueoussodium nitrite solution are are run in. The diazotization solution isthen stirred for 2 hours at from 30° to 35° C. and is filtered, andexcess nitrous acid is destroyed in the conventional manner by addingamidosulfonic acid. The diazonium salt solution thus obtained is thenadded to a solution of 54 parts of4,6-bis-phenoxyethoxypropylamino-2-phenyl-pyrimidine in 700 parts byvolume of isobutanol and 70 parts by volume of 3-normal hydrochloricacid and 1,000 parts of ice, and the pH of the mixture is brought to 5with sodium acetate. After completion of coupling, and after working upin the conventional manner, 48 parts of the dye of the formula given inExample 4 are obtained; this dye dissolves easily in dimethylformamideand polyethylene glycols to give a yellowish red solution and whenprinted, in the form of such a solution or as an aqueous dispersion,onto a polyester or cotton fabric or a polyester/cotton union fabric andafter-treated with hot air or live steam, gives deep clear yellowish redhues.

EXAMPLE 8

12 parts of 3-chloro-4-aminoazobenzene are stirred overnight with 40parts by volume of concentrated hydrochloric acid. 2 parts of anoxyethylated sperm oil alcohol containing about 23 ethylene oxide unitsare then added, the mixture is made up to 400 parts by volume withwater, and 18 parts by volume of a 23% strength sodium nitrite solutionare added to the suspension. After stirring for two hours at 35° C., thesolution is filtered and excess nitrous acid is destroyed in theconventional manner by adding amidosulfonic acid.

The resulting diazonium salt solution is run into 160 parts by volume ofa solution of 18.5 parts of2-phenyl-4-amino-6-phenoxyethoxypropylamino-pyrimidine in isobutanol,whilst adding 300 parts of ice. The pH is brought to about 5 with sodiumacetate. After completion of coupling, the dye is filtered off, washedwith water and dried.

The product, which is in the form of a red powder, is used as an aqueousdispersion or as a solution in a polyethylene glycol to print polyesteror cotton fabrics or polyester/cotton union fabrics, and the print isafter-treated with hot air or live steam. Deep clear red hues of verygood lightfastness and wetfastness are obtained.

Using the same method, with the same diazo component and with thecoupling components shown in the Table below, dyes having similartinctorial properties are obtained.

    __________________________________________________________________________     ##STR39##                                                                    Ex-                                                                           ample                                                                             R.sup.1             R.sup.4                 R.sup.3    Hue                __________________________________________________________________________     9 (CH.sub.2).sub.2OCH.sub.3                                                                          NH(CH.sub.2).sub.2OCH.sub.3                                                                            ##STR40## red                10 (CH.sub.2).sub.3OCH.sub.3                                                                          NH(CH.sub.2).sub.3OCH.sub.3                                                                           "          "                  11                                                                                ##STR41##                                                                                          ##STR42##              "          "                  12                                                                                ##STR43##                                                                                          ##STR44##              "          "                  13                                                                                ##STR45##                                                                                          ##STR46##              "          "                  14 H                    NH.sub.2                "          orange             15                                                                                ##STR47##           NH(CH.sub.2).sub.2O(CH.sub.2).sub.2OH                                                                 "          red                16                                                                                ##STR48##                                                                                          ##STR49##              "          "                  17                                                                                ##STR50##           NH(CH.sub.2).sub.2O(CH.sub.2).sub.2OH                                                                 "          "                  18 "                    NH(CH.sub.2).sub.3OH    "          "                  19                                                                                ##STR51##           NH(CH.sub.2).sub.2OCH.sub.3                                                                           "          "                  20                                                                                ##STR52##           NH(CH.sub.2).sub.2OH    "          "                  21                                                                                ##STR53##             "                     "          "                  22                                                                                ##STR54##                                                                                          ##STR55##              "          "                  23                                                                                ##STR56##           CH.sub.3                N(C.sub.2 H.sub.5).sub.2                                                                 orange             24                                                                                ##STR57##           "                       N(CH.sub.3).sub.2                                                                        "                  25                                                                                ##STR58##           OC.sub.4 H.sub.9        NH(CH.sub.2).sub.2OH                                                                     red                26   "                  OC.sub.2 H.sub.5        NHC.sub.2 H.sub.5                                                                        "                  27 "                    NH.sub.2                NH.sub.2   "                  28 "                    NH(CH.sub.2).sub.2OH    NH(CH.sub.2).sub.2                                                            CH.sub.3   "                  __________________________________________________________________________

example 29

16 parts of o-trifluoromethylaniline are dissolved in 30 parts by volumeof 10-normal hydrochloric acid and 200 parts of water. After adding 200parts of ice, 30 parts by volume of a 23% strength aqueous sodiumnitrite solution are run in under the surface. After stirring for halfan hour at from 0° to 5° C., excess nitrous acid is destroyed in theconventional manner by adding an aqueous solution of amidosulfonic acid.

The solution of the diazonium salt is added to a solution of 30 parts of2-phenyl-4-phenylamino-6-β-hydroxyethylaminopyrimidine in 300 parts byvolume of isobutanol and 100 parts by volume of 3-normal hydrochloricacid. After adding 600 parts of ice, the mixture is buffered to pH 4.5with sodium acetate and the dye suspension is stirred at about 5° C.until coupling has ended. The dye is then filtered off, washed withwater and dried.

20 parts of the resulting coupling product, in 100 parts by volume ofpyridine, are reacted with 11.2 parts by volume of benzoyl chloride for2 hours at 60° C. The solution is then diluted with 200 parts by volumeof methanol and the dye of the formula ##STR59## is filtered off, washedwith methanol and dried. The resulting yellow powder gives a pure yellowsolution in dimethylformamide or polyglycols and, when printed oncotton, polyester or a cotton/polyester union fabric and fixed, givesdeep clear yellow hues which are very fast.

EXAMPLE 30

5.9 parts of o-aminobenzonitrile are initially dissolved in a littleacetone, and then in 150 parts by volume of water and 15 parts by volumeof concentrated hydrochloric acid. 150 parts of ice and 16 parts byvolume of 23% strength sodium nitrite solution are then added and theresulting solution is stirred for 2 hours at about 5° C. Excess nitrousacid is then destroyed with amidosulfonic acid and the diazonium saltsolution is filtered and introduced into a solution of 13.7 parts of2-phenyl-4,6-bis-β-hydroxyethylamino-pyrimidine in 50 parts by volume ofwater and 5 parts by volume of concentrated hydrochloric acid. Afteradding 200 parts of ice, the pH of the mixture is brought to 6 withsodium acetate and the suspension is stirred at 0° C. until coupling hasended. The dye is then filtered off, washed with water and dried.

9 parts of the resulting coupling product, in 200 parts by volume ofchlorobenzene, are boiled for 121/2 hours with 0.5 part ofp-toluenesulfonic acid and 13.7 parts of phenoxyacetic acid. Aftercompletion of the reaction, the dye of the formula ##STR60## isprecipitated with cyclohexane and is purified by dissolving in glacialacetic acid and precipitating with dilute hydrochloric acid. Afterfiltration, washing with water and methanol, and drying, a yellow powderis obtained which gives a neutral yellow solution in polyglycols and,when printed on polyester, cotton or a polyester/cotton union and fixed,gives deep yellow hues with good fastness properties in practical use.

The dyes listed in the Tables which follow are also obtainable by theprocesses described in the preceding Examples:

    ______________________________________                                         ##STR61##                                                                                                  Hue on cotton                                   Ex.  D                       and polyester                                    ______________________________________                                        31   2-chloro-aniline-4-methylsulfone                                                                      yellow                                           32   2-aminodiphenylsulfone  yellow                                           33   3-aminophthalic acid hydroxyethylimide                                                                yellow                                           34   1-aminoanthraquinone    reddish brown                                    35   1-aminoanthraquinone-6-carboxylic acid                                                                reddish brown                                    36   1-amino-2-chloroanthraquinone                                                                         reddish brown                                    37   1-amino-2-bromoanthraquinone                                                                          reddish brown                                    38   1-amino-2,4-dichloroanthraquinone                                                                     reddish brown                                    39   4-amino-3-methoxybenzanthrone                                                                         reddish brown                                    40   2-aminoanthraquinone    red                                              41   2-amino-3-chloroanthraquinone                                                                         red                                              42   2-amino-1-chloroanthraquinone                                                                         red                                              43   2-amino-1-cyano-3-bromo-anthraquinone                                                                 red                                              44   2-amino-3-bromoanthraquinone                                                                          red                                              45   1-aminobenzanthrone     reddish violet                                   46   2-amino-5-chloro-benzophenone                                                                         yellow                                           ______________________________________                                    

    ______________________________________                                         ##STR62##                                                                    Example                                                                                  D                    Hue                                           ______________________________________                                        47                                                                                    ##STR63##              orange                                         48                                                                                    ##STR64##              yellowish red                                  49                                                                                    ##STR65##              yellowish red                                  50                                                                                    ##STR66##              red                                            51                                                                                    ##STR67##              red                                            52                                                                                    ##STR68##              red                                            53                                                                                    ##STR69##              red                                            54                                                                                    ##STR70##              red                                            55                                                                                    ##STR71##              red                                            56                                                                                    ##STR72##              yellowish orange                               57                                                                                    ##STR73##              yellowish orange                               58                                                                                    ##STR74##              yellow                                         59                                                                                    ##STR75##              golden yellow                                  60                                                                                    ##STR76##              orange                                         61                                                                                    ##STR77##              "                                              62                                                                                    ##STR78##              bluish red                                     ______________________________________                                    

    __________________________________________________________________________     ##STR79##                                                                    Example                                                                                D                            Hue                                     __________________________________________________________________________    63                                                                                  ##STR80##                      orange                                   64                                                                                  ##STR81##                      yellowish red                            65                                                                                  ##STR82##                      "                                        66                                                                                  ##STR83##                      "                                        67                                                                                  ##STR84##                      "                                        68                                                                                  ##STR85##                      "                                        69                                                                                  ##STR86##                      "                                        70                                                                                  ##STR87##                      "                                        71                                                                                  ##STR88##                      "                                        72                                                                                  ##STR89##                      "                                        73                                                                                  ##STR90##                      yellow                                   74                                                                                  ##STR91##                      "                                        75                                                                                  ##STR92##                      golden yellow                            76                                                                                  ##STR93##                      golden yellow                            __________________________________________________________________________

    ______________________________________                                         ##STR94##                                                                    Example                                                                                ,  D                    Hue                                          ______________________________________                                        77                                                                                    ##STR95##               reddish orange                                78                                                                                    ##STR96##               red                                           79                                                                                    ##STR97##               "                                             80                                                                                    ##STR98##               "                                             81                                                                                    ##STR99##               "                                             82                                                                                    ##STR100##              reddish orange                                83                                                                                    ##STR101##              reddish orange                                84                                                                                    ##STR102##              golden yellow                                 85                                                                                    ##STR103##              "                                             86                                                                                    ##STR104##              "                                             87                                                                                    ##STR105##              "                                             ______________________________________                                    

    ______________________________________                                         ##STR106##                                                                   example                                                                                  D                     Hue                                          ______________________________________                                        88                                                                                    ##STR107##              reddish orange                                89                                                                                    ##STR108##              red                                           90                                                                                    ##STR109##              "                                             91                                                                                    ##STR110##              "                                             92                                                                                    ##STR111##              "                                             93                                                                                    ##STR112##              reddish orange                                94                                                                                    ##STR113##              reddish orange                                95                                                                                    ##STR114##              golden yellow                                 96                                                                                    ##STR115##              "                                             97                                                                                    ##STR116##              "                                             98                                                                                    ##STR117##              "                                             ______________________________________                                    

    ______________________________________                                         ##STR118##                                                                   example                                                                                  D                     Hue                                          ______________________________________                                         99                                                                                   ##STR119##              yellowish red                                 100                                                                                   ##STR120##              "                                             101                                                                                   ##STR121##              reddish orange                                102                                                                                   ##STR122##              "                                             103                                                                                   ##STR123##              yellow                                        104                                                                                   ##STR124##              golden yellow                                 105                                                                                   ##STR125##              "                                             106                                                                                   ##STR126##              "                                             107                                                                                   ##STR127##              "                                             108                                                                                   ##STR128##              "                                             109                                                                                   ##STR129##              orange                                        110                                                                                   ##STR130##              "                                             111                                                                                   ##STR131##              "                                             ______________________________________                                    

    __________________________________________________________________________     ##STR132##                                                                   example                                                                            R.sup.5            R.sup.4            R.sup.3   Hue                      __________________________________________________________________________    112  CH.sub.3                                                                                          ##STR133##                                                                                       ##STR134##                                                                             yellow                   113  "                                                                                                 ##STR135##                                                                                       ##STR136##                                                                             "                        114  "                                                                                                 ##STR137##        (C.sub.2 H.sub.5).sub.2                                                                 "                        115  (CH.sub.2).sub.2CH.sub.3                                                                         NH(CH.sub.2).sub.3 O(CH.sub.2)OC.sub.4 H.sub.9                                                   N(CH.sub.3).sub.2                                                                       "                        116  NH(CH.sub.2).sub.2OCH.sub.3                                                                      "                                                                                                 ##STR138##                                                                             "                        117  "                                                                                                 ##STR139##        "         "                        118  "                                                                                                 ##STR140##        "         "                        119  "                                                                                                 ##STR141##        "         "                        120  "                                                                                                 ##STR142##        "         "                        121  "                                                                                                 ##STR143##        "         "                        122  "                                                                                                 ##STR144##        "         "                        123                                                                                 ##STR145##                                                                                       ##STR146##                                                                                       ##STR147##                                                                             "                        124  "                  "                                                                                                 ##STR148##                                                                             "                        125  "                  "                                                                                                 ##STR149##                                                                             "                        __________________________________________________________________________

    __________________________________________________________________________     ##STR150##                                                                   Ex.                                                                              R.sup.5              R.sup.4              R.sup.3   Hue                    __________________________________________________________________________    126                                                                              CH.sub.3                                                                                            ##STR151##                                                                                         ##STR152##                                                                             yellow                 127                                                                              "                                                                                                   ##STR153##                                                                                         ##STR154##                                                                             "                      128                                                                              "                                                                                                   ##STR155##          N(CH.sub.3).sub.2                                                                       "                      129                                                                              NH(CH.sub.3).sub.2OCH.sub.3                                                                         ##STR156##                                                                                         ##STR157##                                                                             golden yellow          130                                                                              NH(CH.sub.2).sub.3OCH.sub.3                                                                         ##STR158##          "         orange                 131                                                                              NH(CH.sub.2).sub.2OCH.sub.3                                                                         ##STR159##          "         "                      132                                                                               ##STR160##                                                                                         ##STR161##          "         golden yellow          133                                                                              NH(CH.sub.2).sub.5COOC.sub.2 H.sub.5                                                               NH(CH.sub.2).sub.5COOC.sub.2 H.sub.5                                                               "         "                      134                                                                              NH(CH.sub.2).sub.3OCH.sub.3                                                                         ##STR162##          "         "                      135                                                                               ##STR163##                                                                                         ##STR164##          "         "                      136                                                                               ##STR165##                                                                                         ##STR166##                                                                                         ##STR167##                                                                             "                      137                                                                              "                    "                                                                                                   ##STR168##                                                                             "                      138                                                                              "                    "                                                                                                   ##STR169##                                                                             orange                 139                                                                              NH(CH.sub.2).sub.2OCH.sub.3                                                                         ##STR170##                                                                                         ##STR171##                                                                             golden yellow          140                                                                              "                                                                                                   ##STR172##          "         "                      141                                                                              "                                                                                                   ##STR173##          "         "                      142                                                                              "                                                                                                   ##STR174##          "         "                      __________________________________________________________________________

    __________________________________________________________________________     ##STR175##                                                                   example                                                                            R.sup.4      R.sup.5                 R.sup.3                                                                              Hue                          __________________________________________________________________________    143  NH(CH.sub.2).sub.2OCH.sub.3                                                                NH(CH.sub.2).sub.2OH                                                                                   ##STR176##                                                                          golden yellow                144  "                                                                                           ##STR177##             "      "                            145  "                                                                                           ##STR178##             "      "                            146  "                                                                                           ##STR179##             "      orange                       147  "                                                                                           ##STR180##             "      golden yellow                148  "                                                                                           ##STR181##                    orange                       149  "                                                                                           ##STR182##             "      golden                       __________________________________________________________________________                                                     yellow                   

    __________________________________________________________________________     ##STR183##                                                                   Example                                                                              D                           Hue                                        __________________________________________________________________________    150                                                                                 ##STR184##                   reddish orange                             151                                                                                 ##STR185##                   red                                        152                                                                                 ##STR186##                   "                                          153                                                                                 ##STR187##                   "                                          154                                                                                 ##STR188##                   golden yellow                              155                                                                                 ##STR189##                   "                                          156                                                                                 ##STR190##                   "                                          157                                                                                 ##STR191##                   brownish red                               158                                                                                 ##STR192##                   yellow                                     159                                                                                 ##STR193##                   "                                          160                                                                                 ##STR194##                   "                                          161                                                                                 ##STR195##                   "                                          162                                                                                 ##STR196##                   "                                          163                                                                                 ##STR197##                   "                                          164                                                                                 ##STR198##                   "                                          165                                                                                 ##STR199##                   "                                          166                                                                                 ##STR200##                   "                                          167                                                                                 ##STR201##                   "                                          __________________________________________________________________________

    __________________________________________________________________________     ##STR202##                                                                   Ex-                                                                           am-                                                                           ple                                                                              D                 R.sup.4   R.sup.5      R.sup.3      Hue                  __________________________________________________________________________    168                                                                               ##STR203##       NH(CH.sub.2).sub.2 CH.sub.3                                                             NH(CH.sub.2).sub.2 CH.sub.3                                                                NH(CH.sub.2).sub.2OH                                                                       yellow               169                                                                               ##STR204##       "           "            "          brownish red         170                                                                               ##STR205##       NHC.sub.6 H.sub.5                                                                         "            "          yellow               171                                                                              "                   "       NHC.sub.2 H.sub.5                                                                            "           "                   172                                                                               ##STR206##       NHC.sub.2 H.sub.5                                                                         "          O(CH.sub.2).sub.2 OH                                                                        "                   173                                                                              "                 NHC.sub.6 H.sub.5                                                                       NH.sub.2     NH.sub.2      "                   174                                                                              "                   "       NHC.sub.2 H.sub.5                                                                           ##STR207##   "                   175                                                                              "                   "       O(CH.sub.2).sub.2CH.sub.3                                                                  NH(CH.sub.2).sub.2 OH                                                                       "                   176                                                                              "                   "       NHC.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.5                                                                           "                   177                                                                              "                   "       NH(CH.sub.2).sub.3 CH.sub.3                                                                 ##STR208##   "                   178                                                                               ##STR209##         "                                                                                      ##STR210##                                                                                 ##STR211##   "                   179                                                                               ##STR212##         "       NHCH.sub.3   OC.sub.2 H.sub.5                                                                            "                   180                                                                              "                   "       NHC.sub.2 H.sub.5                                                                          SC.sub.2 H.sub.5                                                                            "                   __________________________________________________________________________     ##STR213##                                                                   Ex-                                                                           am-                                                                           ple                                                                              D                 R.sup.4   R.sup.3      R.sup.5      Hue                  __________________________________________________________________________    181                                                                               ##STR214##       NHC.sub.2 H.sub.4 OCOC.sub.6 H.sub.5                                                    C.sub.6 H.sub.5                                                                            NHC.sub.6 H.sub.5                                                                          orange               182                                                                              "                 NHC.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5                                               "            "          orange               183                                                                              "                 NHC.sub.6 H.sub.5                                                                         "            "          red                  184                                                                              "                 C.sub.6 H.sub.5                                                                         N(C.sub.4 H.sub.9).sub.2                                                                   NHC.sub.2 H.sub.4 OH                                                                       yellow               185                                                                              "                   "         "          NHC.sub.3 H.sub.6 OC.sub.2                                                    H.sub.4 OC.sub.6 H.sub.5                                                                   yellow               186                                                                              "                   "         "          NHC.sub.3 H.sub.6 OCH.sub.3                                                                yellow               187                                                                              "                   "         "          NHC.sub.2 H.sub.4 OCH.sub.3                                                                yellow               188                                                                               ##STR215##       NH.sub.2 H.sub.4 CH.sub.3                                                               C.sub.6 H.sub.5                                                                              "          blue                 189                                                                               ##STR216##       NHC.sub.2 H.sub.4 C.sub.6 H.sub.5                                                         "          NHC.sub.2 H.sub.4 C.sub.6                                                     H.sub.5      blue                 190                                                                              "                 NHC.sub.2 H.sub.4 OH                                                                      "          NHC.sub.3 H.sub.6 OCH.sub.2                                                   C.sub.6 H.sub.5                                                                            blue                 191                                                                               ##STR217##       NHC.sub.2 H.sub.4 OCH.sub.3                                                               "          NHCH.sub.2 C.sub.6 H.sub.5                                                                 blue                 192                                                                               ##STR218##       NH.sub.2    "          NHC.sub.3 H.sub.6 OC.sub.2                                                    H.sub.4 OC.sub.6 H.sub.5                                                                   brown                193                                                                              "                 NHC.sub. 2 H.sub.4 OH                                                                     "          NHC.sub.3 H.sub.6 OCH.sub.2                                                   C.sub.6 H.sub.5                                                                            reddish                                                                       brown                194                                                                              "                 CH.sub.3  N(C.sub.2 H.sub.5).sub.2                                                                   NHC.sub.6 H.sub.5                                                                          orange                                                                        brown                195                                                                              "                  "        N(CH.sub.3).sub.2                                                                            "          brown                196                                                                               ##STR219##       NH.sub.2  C.sub.6 H.sub.5                                                                            NH.sub.2     yellow               197                                                                              "                 CH.sub.3  N(C.sub.2 H.sub.5).sub.2                                                                   NHC.sub.6 H.sub.5                                                                          orange               198                                                                              "                  "        N(CH.sub.3).sub.2                                                                          NHCH.sub.2 C.sub.6 H.sub.5                                                                 orange               199                                                                               ##STR220##        "        N(C.sub.2 H.sub.5).sub.2                                                                   NHC.sub.6 H.sub.5                                                                          red                  200                                                                               ##STR221##                 C.sub.6 H.sub.5                                                                            NH.sub.2     yellow               __________________________________________________________________________

What is claimed is:
 1. Uniformly dyed water-swellable cellulosic fibers,said fibers being fast to washing, dry cleaning, sublimation and light,and having been produced by contacting water-swellable cellulose fiberssequentially or concomitantly with water, ethylene glycol or aderivative thereof and, while the fibers are still swollen with anessentially water-insoluble dye of the formula ##STR222## in which one Ris R¹, or ##STR223## the other R is ##STR224## D is phenyl which issubstituted by cyano, trifluoromethyl, ##STR225## or D is anthraquinonylwhich is unsubstituted or substituted by methyl; R¹ is hydrogen, alkylor 1 to 8 carbon atoms, alkyl of 2 to 8 carbon atoms which issubstituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, benzyloxy orβ-phenylethoxy; phenylakyl (where alkyl is of 1 to 4 carbon atoms),tolylalkyl (where alkyl is of 1 to 4 carbon atoms), phenyl, which isunsubstituted or substituted by methyl, ethyl or R¹ is (CH₂)₃ OC₂ H₄ C₆H₅ ;R² is hydrogen, alkyl of 1 to 8 carbon atoms, or alkyl of 2 to 9carbon atoms substituted by hydroxyl or alkoxy of 1 to 8 carbon atoms,T¹ is hydrogen, chlorine, bromine, methyl, methoxy or ethoxy, T² ishydrogen, methyl, methoxy or ethoxy, T³ is hydrogen, methyl, chlorine,bromine, nitro, T⁴ is hydrogen, chlorine or bromine and T⁵ is hydrogen,methyl or ethyl.
 2. The dyed fibers according to claim 1, wherein D isphenyl substituted by cyano, trifluoromethyl, ##STR226## oranthraquinonyl, R¹ is hydrogen, C₁ to C₈ alkyl, C₂ to C₈ alkylsubstituted by hydroxy, C₁ to C₄ alkoxy, benzyloxy, β-phenylethoxy;phenyl-C₁ to C₄ -alkyl; phenyl, phenyl substituted by methyl or R¹ is(CH₂)₃ (OC₂ H₄)OC₆ H₅,R² is hydrogen, alkyl of 1 to 8 carbon atoms,alkyl of 2 to 9 carbon atoms substituted by hydroxyl or alkoxy of 1 to 8carbon atoms, T¹ is hydrogen, chlorine, bromine, methyl, methoxy orethoxy, T² is hydrogen, methyl, methoxy or ethoxy, T³ is hydrogen,methyl, chlorine, bromine, nitro, T⁴ is hydrogen, chlorine or bromineand T⁵ is hydrogen, methyl or ethyl.
 3. The fibers according to claim 1dyed with a dye of the formula ##STR227## where p is 0 or
 1. 4. Thefibers according to claim 1 dyed with a dye of the formula ##STR228##where p is 0 or 1 andD is ##STR229##
 5. The fibers according to claim 1dyed with a dye of the formula ##STR230##
 6. The fibers according toclaim 1, wherein said fibers consist essentially of cotton.
 7. Thefibers according to claim 1, wherein said fibers comprise a mixture ofcotton and polyester.
 8. Printed fibers according to claim 1.